Phase-change behavior and nonlinear optical second and third harmonic generation of the one-dimensional K(1- x)CsxPSe6 and metastable β-CsPSe6

Alyssa S. Haynes, Felix O. Saouma, Calford O. Otieno, Daniel J. Clark, Daniel P. Shoemaker, Joon I. Jang, Mercouri G Kanatzidis

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Abstract

The APSe6 (A = K, K(1-x)Csx, Cs) family of one-dimensional (1D) materials was studied to examine the effects of the cation size on the nonlinear optical (NLO) response. The family has high-performing NLO properties with the noncentrosymmetric parent material, KPSe6, having infinite 1D chains of 1/[PSe6-]. This structure has been successfully substituted with cesium up to K0.6Cs0.4PSe6 while retaining the polar character. All compounds crystallize in the space group Pca21 and have band gaps of 2.1 eV. In situ powder X-ray diffraction experiments using synchrotron radiation were used to determine the specifics of the amorphous to crystalline behavior and the crystallization and melting kinetics of the APSe6 system. These measurements revealed a new phase, β-CsPSe6, which is metastable and crystallizes in the noncentrosymmetric tetragonal space group P 4 21c with a = 12.526(2) Å, c = 12.781(3) Å, V = 2005.3(6) Å3, and Z = 8. The structure is composed of 2 sets of mutually perpendicular 1/[PSe6-] chains charge-balanced by Cs cations, and the band gap of β-CsPSe6 is 1.9 eV. Second harmonic generation (SHG) measurements demonstrate that substitution of Cs into KPSe6 maintains the strong NLO signal with a very high SHG coefficient (χ(2)) of ∼ 150 pm/V for K(1-x)CsxPSe6 and 30 pm/V for β-CsPSe6. Laser-induced damage threshold analysis reveals APSe6 exhibits two-photon absorption (2PA) at 1064 nm with input laser intensity greater than 1 GW/cm2 and optical damage from 2PA at ∼ 2 GW/cm2. The materials also exhibit strong third harmonic generation (THG) with THG coefficients (χ(3) × 105) for KPSe6, K0.6Cs0.4PSe6, α-CsPSe6, and β-CsPSe6 to be 2.6, 3.1, 1.8, and 1.1 pm2/V2, respectively.

Original languageEnglish
Pages (from-to)1837-1845
Number of pages9
JournalChemistry of Materials
Volume27
Issue number5
DOIs
Publication statusPublished - Mar 10 2015

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Harmonic generation
Cations
Energy gap
Positive ions
Laser damage
Cesium
Crystallization
Synchrotron radiation
X ray powder diffraction
Melting
Substitution reactions
Photons
Optical properties
Crystalline materials
Kinetics
Lasers
Experiments

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

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Phase-change behavior and nonlinear optical second and third harmonic generation of the one-dimensional K(1- x)CsxPSe6 and metastable β-CsPSe6. / Haynes, Alyssa S.; Saouma, Felix O.; Otieno, Calford O.; Clark, Daniel J.; Shoemaker, Daniel P.; Jang, Joon I.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 27, No. 5, 10.03.2015, p. 1837-1845.

Research output: Contribution to journalArticle

Haynes, Alyssa S. ; Saouma, Felix O. ; Otieno, Calford O. ; Clark, Daniel J. ; Shoemaker, Daniel P. ; Jang, Joon I. ; Kanatzidis, Mercouri G. / Phase-change behavior and nonlinear optical second and third harmonic generation of the one-dimensional K(1- x)CsxPSe6 and metastable β-CsPSe6. In: Chemistry of Materials. 2015 ; Vol. 27, No. 5. pp. 1837-1845.
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abstract = "The APSe6 (A = K, K(1-x)Csx, Cs) family of one-dimensional (1D) materials was studied to examine the effects of the cation size on the nonlinear optical (NLO) response. The family has high-performing NLO properties with the noncentrosymmetric parent material, KPSe6, having infinite 1D chains of 1/∞[PSe6-]. This structure has been successfully substituted with cesium up to K0.6Cs0.4PSe6 while retaining the polar character. All compounds crystallize in the space group Pca21 and have band gaps of 2.1 eV. In situ powder X-ray diffraction experiments using synchrotron radiation were used to determine the specifics of the amorphous to crystalline behavior and the crystallization and melting kinetics of the APSe6 system. These measurements revealed a new phase, β-CsPSe6, which is metastable and crystallizes in the noncentrosymmetric tetragonal space group P 4 21c with a = 12.526(2) {\AA}, c = 12.781(3) {\AA}, V = 2005.3(6) {\AA}3, and Z = 8. The structure is composed of 2 sets of mutually perpendicular 1/∞[PSe6-] chains charge-balanced by Cs cations, and the band gap of β-CsPSe6 is 1.9 eV. Second harmonic generation (SHG) measurements demonstrate that substitution of Cs into KPSe6 maintains the strong NLO signal with a very high SHG coefficient (χ(2)) of ∼ 150 pm/V for K(1-x)CsxPSe6 and 30 pm/V for β-CsPSe6. Laser-induced damage threshold analysis reveals APSe6 exhibits two-photon absorption (2PA) at 1064 nm with input laser intensity greater than 1 GW/cm2 and optical damage from 2PA at ∼ 2 GW/cm2. The materials also exhibit strong third harmonic generation (THG) with THG coefficients (χ(3) × 105) for KPSe6, K0.6Cs0.4PSe6, α-CsPSe6, and β-CsPSe6 to be 2.6, 3.1, 1.8, and 1.1 pm2/V2, respectively.",
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T1 - Phase-change behavior and nonlinear optical second and third harmonic generation of the one-dimensional K(1- x)CsxPSe6 and metastable β-CsPSe6

AU - Haynes, Alyssa S.

AU - Saouma, Felix O.

AU - Otieno, Calford O.

AU - Clark, Daniel J.

AU - Shoemaker, Daniel P.

AU - Jang, Joon I.

AU - Kanatzidis, Mercouri G

PY - 2015/3/10

Y1 - 2015/3/10

N2 - The APSe6 (A = K, K(1-x)Csx, Cs) family of one-dimensional (1D) materials was studied to examine the effects of the cation size on the nonlinear optical (NLO) response. The family has high-performing NLO properties with the noncentrosymmetric parent material, KPSe6, having infinite 1D chains of 1/∞[PSe6-]. This structure has been successfully substituted with cesium up to K0.6Cs0.4PSe6 while retaining the polar character. All compounds crystallize in the space group Pca21 and have band gaps of 2.1 eV. In situ powder X-ray diffraction experiments using synchrotron radiation were used to determine the specifics of the amorphous to crystalline behavior and the crystallization and melting kinetics of the APSe6 system. These measurements revealed a new phase, β-CsPSe6, which is metastable and crystallizes in the noncentrosymmetric tetragonal space group P 4 21c with a = 12.526(2) Å, c = 12.781(3) Å, V = 2005.3(6) Å3, and Z = 8. The structure is composed of 2 sets of mutually perpendicular 1/∞[PSe6-] chains charge-balanced by Cs cations, and the band gap of β-CsPSe6 is 1.9 eV. Second harmonic generation (SHG) measurements demonstrate that substitution of Cs into KPSe6 maintains the strong NLO signal with a very high SHG coefficient (χ(2)) of ∼ 150 pm/V for K(1-x)CsxPSe6 and 30 pm/V for β-CsPSe6. Laser-induced damage threshold analysis reveals APSe6 exhibits two-photon absorption (2PA) at 1064 nm with input laser intensity greater than 1 GW/cm2 and optical damage from 2PA at ∼ 2 GW/cm2. The materials also exhibit strong third harmonic generation (THG) with THG coefficients (χ(3) × 105) for KPSe6, K0.6Cs0.4PSe6, α-CsPSe6, and β-CsPSe6 to be 2.6, 3.1, 1.8, and 1.1 pm2/V2, respectively.

AB - The APSe6 (A = K, K(1-x)Csx, Cs) family of one-dimensional (1D) materials was studied to examine the effects of the cation size on the nonlinear optical (NLO) response. The family has high-performing NLO properties with the noncentrosymmetric parent material, KPSe6, having infinite 1D chains of 1/∞[PSe6-]. This structure has been successfully substituted with cesium up to K0.6Cs0.4PSe6 while retaining the polar character. All compounds crystallize in the space group Pca21 and have band gaps of 2.1 eV. In situ powder X-ray diffraction experiments using synchrotron radiation were used to determine the specifics of the amorphous to crystalline behavior and the crystallization and melting kinetics of the APSe6 system. These measurements revealed a new phase, β-CsPSe6, which is metastable and crystallizes in the noncentrosymmetric tetragonal space group P 4 21c with a = 12.526(2) Å, c = 12.781(3) Å, V = 2005.3(6) Å3, and Z = 8. The structure is composed of 2 sets of mutually perpendicular 1/∞[PSe6-] chains charge-balanced by Cs cations, and the band gap of β-CsPSe6 is 1.9 eV. Second harmonic generation (SHG) measurements demonstrate that substitution of Cs into KPSe6 maintains the strong NLO signal with a very high SHG coefficient (χ(2)) of ∼ 150 pm/V for K(1-x)CsxPSe6 and 30 pm/V for β-CsPSe6. Laser-induced damage threshold analysis reveals APSe6 exhibits two-photon absorption (2PA) at 1064 nm with input laser intensity greater than 1 GW/cm2 and optical damage from 2PA at ∼ 2 GW/cm2. The materials also exhibit strong third harmonic generation (THG) with THG coefficients (χ(3) × 105) for KPSe6, K0.6Cs0.4PSe6, α-CsPSe6, and β-CsPSe6 to be 2.6, 3.1, 1.8, and 1.1 pm2/V2, respectively.

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